Pentachlorobenzenethiolmethyl substituted organosiloxanes



PENTACHLOROEENZENETHIOLMETHYL SUBSTITUTED ORGANOSILOXANES Robert L. Marker, Pittsburgh, Pa., assignor to Dow Corning Corporation, Midland, Mich, a corporation of Michigan No Drawing. Application July 5, 1957 Serial No. 669,939

7 Claims. (Cl. 260-4482) The present invention relates to pentachlorobenzenethiolmethyl substituted organosiloxanes, i. e. siloxanes containing the grouping SCH attached to at least some of the silicon atoms therein.

Organosiloxane liquids and their desirable properties of inertness, low viscosity-temperature slope, thermal stability, etc. are well known. Their lubricating qualities, however, are in general relatively poor as compared to organic lubricants. It is a major object of this invention to provide novel organosiloxanes of greatly improved ability to lubricate metal surfaces, or which can be added to conventional organosiloxanes to improve the lubricating qualities of the latter. Other objects and advantages will be apparent from the following specification.

This invention is particularly concerned with a pentachlorobenzenethiolmethyl substituted organosiloxane in which at least 0.1 molar percent of the siloxane units present are of the formula (Cl O6SCH )R,,SiO T where x is an integer of from 1 to 2 inclusive and R is a radical selected from the group consisting of alkyl and aryl radicals, any other siloxane units present being of the formula R SiO 2 where y is an integer of from 1 to 3 inclusive and R is a radical selected from the group consisting of alkyl, aryl, haloalkyl, and haloaryl radicals, said organosiloxane having an average of from 1.9 to 3 inclusive total organic groups attached to silicon per silicon atom.

From the above definition it can be seen that from 0.1 to 100 percent of the Si atoms present in the organosiloxane contain one Cl C SCH group attached thereto. Each Si atom so substituted must also have either 1 or 2 alkyl and/or aryl radicals attached thereto by C-Si linkage. If any other organosiloxane units are present in the polymer, each such unit can contain 1, 2 or 3 organic radicals attached to the Si atom therein by C-Si linkage, and said radicals can be alkyl, aryl, haloalkyl, or haloaryl radicals alone or in any combination. When such other units are present, however, they must be of a type and present in an amount such that the average degree of substitution ranges from 1.9 to 3 inclusive. In other words, the average ratio of total organic groups per silicon atom (i. e. R 'groups plus R groups plus Cl C SCH groups divided by total Si atoms) must be from 1.9 to 3.

The organosiloxanes of this invention can be prepared by reacting the sodium salt of pentachl'orobenzenethiol with an organosiloxane which contains a C1CH group attached to those silicon atoms which one wishes to subtatcs atent 2,853,898 Patented Dec. 9, 1958 stitute with the Cl C SCH group. Thus the reaction in simplified form can be represented as follows:

In the above equation, the open valences of Si which are not satisfied by l or 2 R groups are satisfied by oxygen atoms which in turn are attached to other silicon atoms.

Even the most complex copolymers of this invention can be prepared by the single reaction described above by choosing the corresponding ClCH substituted organosiloxane as a reactant, and a wide variety of such shortanes are known to the art. It is preferable, however, to prepare such complex copolymers by reacting the sodium salt with a relatively simple ClCH substituted organosiloxane, followed by equilibrating or copolymerizing the resulting product with a conventional organosiloxane which contains the other organic groups desired in the final product. The usual well known siloxane polymerization catalysts and techniques can be used in the latter steps.

Thus, for example, the thiol salt can be reacted with a disiloxane of the formula (CICH R SD O to produce the corresponding derivative of the formula (ZR SD O, where Z represents the Cl' C SCH group. The latter derivative can then be equilibrated with any organosiloxane containing RSiO R' SiO, or R' SiO units in any combination suitable to provide the required minimum degree of substitution of 1.9. Likewise the thiol salt can be reacted with, e. g., a linear organosiloxane containing repeating units of the formula ClCH RSiO, or a cyclic compound such as (ClCH RSiO) or to produce the corresponding derivatives containing ZRSiO units alone or together with R SiO units. These derivatives can then be equilibrated with the conventional organosiloxanes as previously discussed.

The R and R radicals are inert throughout the salt reaction and equilibration, hence those radicals which are originally present in the reactants will be found in the product. As noted previously, the R radicals are alkyl and/or aryl radicals. Examples of the former include such illustrative species as methyl, ethyl,-propyl, octadecyl, cyclohexyl, and benzyl. Suitable aryl radicals include phenyl, tolyl, Xenyl, and naphthyl. The chloromethyl substituted siloxanes can be prepared, e. g., by hydrolyzing or cohydrolyzing CICH RSiCI or ClCH R SiC1 compounds, or by cohydrolyzing. either or both of such compounds with one or more R' SiCl type compounds, y being 1, 2, or 3. The chloromethylchlorosilanes used in the above hydrolyses are known compounds, and can be prepared, e. g., by chlorinating the corresponding CH R SiCl compounds or by chlorinating CH SiCl to form C1CH SiCl followed by the reaction of the latter with the appropriate Grignard reagent to introduce any desired R groups. For ease of preparation, availability, and superior properties, it is preferred that R be methyl and/ or phenyl.

The conventional organosiloxane polymers used herein for equilibration are of course well known, and many are commercially available. These polymers have the average general formula R SiO 2 where y has a value from 1 to 3 inclusive. The R radicals can be alkyl or aryl (suitable species being the same as the illustrative R radicals given above); such as chloromethyl and 1,1,1-trifluoropropyl; or haloaryl such as chlorophenyl, bromophenyl, dichlorophenyl, tetrachloroxenyl, and a,a,a-trifiuorotolyl. These convenor haloalkyl.

tional" organosiloxane polymers should either be liquid or capable of being dissolved in inert organic solvents such as benzene, toluene, or xylene, so that they can be intimately mixed with the Cl C SCI-I -substituted poly mers for equilibration purposes. They also can contain uncondensed silicon-bonded OH groups, as is particularly common among those polymers having an average degree of substitution of less than 2.

When equilibration techniques are used herein, the reactants are intimately mixed (using an organic solvent if necessary) in the presence of a siloxane polymerization catalyst. Concentrated sulfuric acid and trifluoroacetic acid are preferred examples of suitable catalysts, and they can be used, c. g., in amounts of from 0.5 to 5% by weight based on the weight of the siloxanes present. The H equilibration often proceeds at room temperature, but can be expedited at elevated temperatures, e. g. 50 to 175 C. It is to be understood that the term polymer is used herein as inclusive of dimers and copolymers. Thus the invention includes dimers such as (ZMe Si) O,

(ZMePhSD O. ZPh SiOSiMe Z, ZMe SiOSiMe ZIvIePhSiOSiIVIe Ph, and (ZMeEtSi) )O (For simplicity, the symbols Z, Me, Et, and Ph are used above, and hereafter in this specification, as Cl C SCH methyl. ethyl, and phenyl radicals respectively.) The invention also includes true polymers in the narrower sense, such as siloxanes of the formulas (ZMeSiO),,, (ZEtSiO) and (ZPhSiOL These may be in the form of cyclic ZMe- SiOCWe SiO) SiMe ZMe SiO(Me SiO)SiMe Z, ZMePhSiO(Me SiO)SiMePhZ, and ZPh SiO(PhMeSiO) sir n 2 This type also includes the high polymers such as those of the general formulas ZMe SiO(Me SiO) SiMe Z,

ZMePhSiO (Me SiO) SiMe Z, Zl Ie SiO(Me SiO (MePhSiO SiMe Z, and ZMe SiO (Me SiO) (Cl C -H MeSiO SiMe Z In these polymers, d and a can be any integer so long as the required 0.1 molar percent of Z-containing units is present, i. e. the average sum of d plus 2 is not more than 21000. Where more than one type of R' SiO unit occurs 1n the above formulas, each will of course appear throughout the molecule in a random pattern of distribution and not in the grouped pattern which is shown above for convenience.

All of the above polymers containing the Z group in the end-blocking unit can be defined as linear polymers of one or more R' SiO units end-blocked with ZR SiO units. For lubricant purposes, the most practical range of viscosities is obtained when the latter units are present in an amount of from 1 to 10 inclusive molar percent. The best viscosity-temperature slope characteristics are obtained when all R and R radicals are methyl, but thermal stability is improved when at least some of the R and/or R radicals are phenyl. Thus one preferred type of copolymer is one in which the units consist essentially of from 0.1 to 10 inclusive molar percent of units of the formula (Cl C SCH )Me SiO from 1 to 99.9 inclusive molar percent of units of the formula PhMeSiO, and from 0 to 93 inclusive molar percent of units of the formula Me SiO. Preferably there is at least 10 molar percent of the latter units present, in which case there will be a maximum of 89.9 mol percent of the PhMeSiO units.

The lubricating qualities of the products of this invention can be further improved in regard to some metal surfaces by incorporating siloxane units which have haloaryl radicals directly attached to the Si atom. The chlorine or bromine substituted phenyl or xenyl radicals described in Fletcher and Hunter Patent No. 2,599,984, issued June 10, 1952, are particularly effective and are preferred. The best form of the modification in question is that in which the copolymer contains (A) from 0.1 to 10 inclusive mol percent of ZMe SiO, units, (B) from 70 to 99.8 inclusive mol percent of Me SiO units, (C) from O to inclusive mol percent of (Ci CGI'I5 )I\ICSiO units where a is 1 or 2, and (D) from 0 to 10 mol percent of (Cl C H )SiO units where b is l or 2, there being from 0.1 to 20 inclusive mol percent of (C) plus (D) units. In other words, there can be present up to 20 mol percent of the di-substituted" (ClC l ifli leSiO units and/or (Cl C H )MeSiO units, or alternatively up to 10 mol percent of the m0nosubstituted (ClC H.-,)SiO and (Cl C H )SiO units, or any combination of any of the four units so long as the polymer contains at least 0.1 mol percent of at least one of the units and not more than the defined maximum of (C) or (D) or (C) plus (D) units.

A still further type of polymer within the scope of the invention is one in which ZRSiO units, either with or without additional R SiO units, form the repeating units in a linear chain which is end-blocked with R' SiO units. The preferred form of this type of polymer is one which contains from 0.1 to 99 inclusive mol percent of ZMeSiO units, from 1 to 66% inclusive mol percent Me SiO units, and from O to 98.9 inclusive mol percent Me SiO units. For the best temperature-viscosity slope characteristics, it is preferred that there be at least 70 mol percent of the latter units, in which case there would of course be a maximum of 29.9 mol percent of the Me siO units. The thermal stability of this type of polymer can be increased by incorporating PhMeSiO and/or Ph SiO units in amounts up to, e. g., of the total R SiO units present. It is also possible to modify the lubricity characteristics of this type of polymer by incorporating haloaryl substituted siloxane units, e. g. ClC H MeSiO and/or CIQCGE'IgRICSlO units in amounts up to 20 mol percent, or ClC -kl SiO and/or Cl C H SiO units in amounts up to 10 mol percent of the total siloxane units present. As with the similarly modified polymers discussed previously, within the defined limits any combination of any of these four units can be present but it is preferred that the total not exceed 20 mol percent.

The products of this invention vary from relatively low viscosity liquids to non-flowing gums, and include crystalline materials as well. The liquid materials are useful as oily lubricants per se and as bases to which conventional grease forming or thickening agents can be added. Examples of such agents include silica. alkali metal and alkaline earth salts of fatty acids such as lithium stearate, hydroxystearic acid salts, carbon black, alkali metal and alkaline earth metal salts of alicyclic substituted fatty acids having a chain length of 1 to 6 carbon atoms, etc. as has been extensively documented in the organosiloxane patent literature (see, c. g., the aforesaid U. S. Patent No. 2,599,984). Gums prepared in accordance with this invention can be mixed with suitable fillers (e. g. fume silica, silica aerogel, diatomaceous earth, titania, ferric oxide, and the like) and cured or vulcanized by the usual techniques to form silicone rubbers having modified properties, e. g. solvent-swelling characteristics. The utility of the crystalline products lies largely in their use as reactants in equilibration processes to form other silicone products.

It is to be understood that the polymers of the present as esses d invention can contain small amounts (usually less than 0.3 percent by weight) of uncondensed silicon-bonded hydroxy groups or unhydrolyzed silicon-bonded hydrolyzable groups (e. g. C1 or alkoxy groups) carried over from the intermediate monomers from which the polymers have been prepared. The presence of such groups is, of course, not at all uncommon in conventional organosiloxanes.

The following examples are illustrative only. All parts are parts by weight unless otherwise indicated.

Example 1 Pentachlorobenzenethiol was neutralized to a pH of 10 by the addition of a solution of NaOH in isopropyl alcohol. The resulting salt slurry was devolatilized and dried at 80 C., and 2 moles of the salt was reacted with 1 mole of (ClCH Me SD O in times the latters weight of dimethylformamide by heating the mixture at reflux temperature. A quantitative amount of NaCl was removed from the reaction product by filtration, then the filtrate was diluted with benzene and washed with water. The dimeric product [(Cl C SCH )Me Si] O was precipitated from the benzene in 85% yield. Recrystallization from acetone gave a product with a melting point of 111.5 C.

Example 2 A mixture was prepared containing 16.4 parts of the product of Example 1, 44 parts benzene, 67.25 parts of the cyclic (Me SiO) and 2 parts concentrated sulfuric acid. The starting siloxanes provided a ratio of two (Cl C SCH )Me SiO groups per 40 Me SiO groups. This mixture was warmed at 50 C. for a total of 40 hours, complete solution of the dimer being obtained during the first 20 hours. The resulting equilibration product was further diluted with benzene and washed with a dilute aqueous solution of sodium bicarbonate until free of acid, then further washed with water alone. The benzene was removed by distillation and the resulting fluid product was further devolatilized at 100 C. under reduced pressure. The final fluid product had a viscosity of 90.45 cs. at 25 C., n 1.4340, (1 1.059. Analysis showed 31.53% by weight Si in the product, as compared to the 31.93% Si calculated for a polymer having the average formula 4gSiMe2 The lubricating properties of the fluid product were tested in the well known Shell four-ball wear test. After 2 hours at 1200 R. P. M. under a 40 kg. load and at a test temperature of 275 R, an average scar diameter of only 0.92 mm. was obtained. In comparison, a fluid containing Cl C -H MeSiO units in an amount of mol percent, the remaining units being Me SiO and Me SiO units, gave a scar diameter of 2.0 mm. in the same test. A fluid of comparable viscosity containing only Me SiO and Me SiO units is relatively so poor a lubricant for steel-on-steel that seizure occurs and a comparable test cannot even be run.

Example 3 Using the equilibration technique of Example 2,

was reacted with various other siloxanes to form the corresponding copolymers. Thus when 1 mole of the dimer is reacted with 10 moles (PhMeSiO) the resulting copolymer has the average formula where Z is the Cl C SCH radical. When the dimer is reacted with (Me SiO) in the molar ratio of 1:500, a copolymer with the average formula is obtained as a very viscous liquid. When 1 mole of the dimer is reacted with 5 moles (Me SiO), and 5 moles (PhMeSiO) the liquid copolymeric product has the average formula ZMe SiO(Me Si0) (PhMeSi0)2uSiMe Z.

Example 4 A mixture of 1 mole Cl C H SiCl 1 mole clgcsHgMesiclz and 7 moles Me SiCI- was mixed with an equal weight of toluene and cohydrolyzed by adding it to an excess of cold water. The toluene solution of cohydrolyzate was heated to reflux temperature, and then was Washed free of acid. When this cohydrolyzate is mixed with 0.5 mole of the dimer product of Example 1 and equilibrated by the method of Example 2, a copolymeric liquid is obtained containing 10 mol percent Cl C H SiO units, 10 mol percent CI C H MeSiO units, 70 mol percent Me SiO units, and 10 mol percent (Cl C SCH )Me SiQ units.

Example 5 When 1 mole of ClCH Me SiOSiMe is reacted with 1 mole of the sodium salt of pentachlorobenzenethiol by the method of Example 1, the product by the method of Example 2, a mixture of copolymers is obtained, some being of the type Me SiO Me SiO SiMe some of the type ZMe SiO(Me SiO) SiMe Z, and some of the type ZMe SiO(Me- Si0) SiMe where Z is CI C SCH and d represents the degree of polymerization.

Example 6 When 1 mole of (ClCH MePhSi) O is reacted with 2 moles of the salt of Example 1, the resulting product has the formula (ZMePhSi) O where Z is Cl C SCH When the latter product is equilibrated with (Me SiO) as in Example 2, the copolymeric product is a liquid having the average formula ZMePhSiO(Me SiO) SiMePhZ Example 7 When 1 mole of the salt of Example 1 is reacted as in that example with 1 mole of the compound When 1 mole of the salt of Example 1 is reacted with 1 mole of chloromethylheptamethylcyclotetrasiloxane, i. e.

ClCHzMeSlO (MezSiOhMBzSiO the corresponding cyclic compound ZMeSiO(MegSiO)2Me2S1O is obtained, where Z is the Cl C SCH radical. When hexamethyldisiloxane is equilibrated with the latter in the molar ratio of 1:2 by the method of Example 2, a liquid having the average formula Me SiO(ZMeSiO) (Me SiO) SiMe is obtained. If the compound Me Si0(ClCI-I MeSiO)SiMe is used in place of the hexamethyldisiloxane in the above Me PhSiO(ZMeSiO) SiMe Ph Equilibration with an excess of hexatncthyldisiloxane produces the linear trimer Me SiO(ZMeSiO)SiMe That which is claimed is:

l. A pcntachlorobenzenethiolmethyl substituted organosiloxane in which at least 0.1 molar percent of the siloxane units present are of the formula where x is an integer of from 1 to 2 inclusive and R is a radical selected from the group consisting of alkyl and aryl radicals, any other siloxane units present in the organosiloxane being of the formula where y is an integer of from 1 to 3 inclusive and R is a radical selected from the group consisting of alkyl, aryl, haloalkyl, and haloaryl radicals, said organosiloxane having an average of from 1.9 to 3 inclusive total Organic groups attached to silicon per silicon atom.

2. An organodisiloxane having the formula 3. An organosiloxane linear polymer in which the repeating units are of the formula (CH S1O and the endblocking units are of the formula (CI C SCH (CH SiO the latter being present to the extent of at least 0.1 molar percent of the total siloxane units.

4. A linear polymer in accordance with claim 3 wherein the (Cl C SCH )(CH SiO units represent from 1 to 10 inclusive molar percent of the total siloxane units.

5. An organosiloxane in which the polymeric units consist essentially of from 0.1 to 10 inclusive molar percent of units of the formula (Cl C SCH )(CHQ SiO from 1 to 99.9 inclusive molar percent of units of the formula (C H )(CH )SiO, and up to 98 inclusive molar percent of units of the formula (CH SiO.

6. An organopolysiloxane in which the polymeric units consist essentially of (A) from 0.1 to 10 inclusive molar percent of units of the formula (Cl C SCH (Cl-l SiO (B) from 70 to 99.8 inclusive molar percent of units of the formula (CH SiO, (C) up to 20 inclusive molar percent of units of the formula (Cl C H )CH SiO where u is l to 2 inclusive, and (D) up to 10 inclusive molar percent of units of the formula (CI C H JSiO where I) is 1 to 2 inclusive, the total of (C) and (D) units present being from 0.1 to 20 inclusive molar percent of the total siloxane units present and there being at least as many (A) units as (D) units in the polymer.

7. An organopolysiloxane in which the polymeric units consist essentially of from 0.1 to 99 inclusive molar percent of units of the formula (C1 C SCH )CH SiO, from i to 66 /3 inclusive molar percent of units of the formula (CH SiO and up to 98.9 inclusive molar percent of units of the formula (CH SiO.

References Cited in the file of this patent UNITED STATES PATENTS 2,544,296 Burkhard Mar. 6, 1951 2,604,486 Burkhard July 22, 1952 2,719,165 Cooper Sept. 27, 1955 2,802,853 George Aug. 13, 1957 OTHER REFERENCES I. A. C. 8., vol. 75, pages 3760-3762 UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,863,898 December 9, 1958 Robert L. Merker It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 3, the right-hand portion of the equation should read as shown below instead of as in the patent- Cl C SOH Si +NaGl column 3, line 23, for (ZMeEtSi) 0 read -(ZMeEtSi) O-; line 44, for high read -higher-; column 4, line 22, for and (C1 C H )SiO read -and/or (C12C6H3) Sl01 5'';

column 5, line 45, right-hand portion of the formula, for (CH SC SL) read -(CH SC6C1 Signed and sealed this 7th day of April 1959.

Attest= KARL H. AXLINE, ROBERT C. WATSON, Attestz'ng Ofiicer. Oommz'ssz'oner of Patents. 

1. A PENTACHLOROBENZENETHIOLMETHYL SUBSTITUTED ORGANOSILOXANE IN WHICH AT LEAST 0.1 MOLAR PERCENT OF THE SILOXANE UNITS PRESENT ARE OF THE FORMULA 